Polyalcohol-fatty acid-aliphatic amine combinations useful as textile assistants andprocess of producing the same



Patented Dec. 20, 1949 POLYALCOHOL-FATTY AClD-ALIPHATIC AMINE COMBINATIONS USEFUL as rax- .lILE ASSISTANTS AND PRODUCING THE SAME PROCESS OF Alton A. Cook. Glen Ridge, and Ira Sapers, Newark, N. J assignors Newark. N. J.,

to Arkansas Company, Inc., a corporation of New York No Drawing. Application May 12, 1947, Serial No. 747,598

Claims. (01. 260-404) The present invention relates to textile assistants and processfor manufacturing the same, and it particularly relates to such assistants havin: particular utility as detergents, wetting agents and emulsifying agents. It is among the objects of the present invention to provide a novel procedure and novel combinations by such procedure which at low cost will give a high yield of unusually effective detergent, wetting and emulsifying agents particularly useful in the textile field, but also useful in the leather, metal working and other allied fields.

Still further objects and advantages will appear in the more detailed description set forth below, it being understood, however, that this more detailed description is given by way of illustration and explanation only and not by way of limitation, since various changes may be made therein by those skilled in the art without departing from the scope and spirit of the present invention.

In the preferred procedure, a high molecular weight fatty acid is combined at a relatively low temperature, for example below 135 C., in two steps, first with a polyethylene glycol and then in a second step the combination of fatty acid and polyethylene glycol is combined with an aliphatic amine, preferably either an alkanolamine or a polyalkylene polyamine. The second step is usually carried on at a temperature 10 C. to C.

higher than the temperature employed in the first step.

As an alternative procedure, the fatty acid is combined in the first step with the amine at a temperature below 135 C. and then in a second step the fatty acid-amine condensation product is further combined with the polyethylene glycol at a slightly lower temperature.

The resulting product is highly complex and, roughly estimating the compositions by active grouping present, the compound may be regarded as composed of:

(I) 80% to 80% of the fatty acid esterified including both amino esters and polyglycol esters;

(II) 1% to 10% of the fatty acid in the form of amide;

(III) 10% to of the fatty acid in the form of a soap.

This complex may be neutralized or acidified with lower aliphatic acids, such as formic or acetic. 1

The complex may also be treated with alkylatin: agents, including methyl iodide, dietbyl sul- 2 phate or dimethyl sulphate, in alkaline media up to 100 C. with or without presence of solvents.

It has been found in the present invention that where these two types of reactions are carried out by a definite succession of steps under controlled conditions, products are obtained which have properties which would not be expected from a physical mixture. of an amino fatty acid condensation product and a polyethylene glycolfatty acid ester.

The ingredients used in this invention fall into three classes of compounds and at least one compound of each class is necessary to the manufacture of the products described herein.

Class 1.Fatty acids having from 8 to 24 carbon atoms. The saturated fatty acids Cm to 01s are preferred but the unsaturated and hy'droxylated types may be used. This includes mixed fatty acids obtained from splitting natural oils and fats.

Example.-Capric, lauric, myristic, palmitic and stearic acids are preferred. Oleic, ricinoleic, erucic, and mixed fatty acids from coconut palm oil, tallow and Japan wax may also be used.

2 Coconut fatty acids on the average contain about 45 to of the C1: acid which is lauric, about 15 to 25% of the C14 acid which is myristic, about 5 to 10% of the C10 acid which is capric, and about 5 to 10% of oleic (see Vegetable Fats and Oils, George S. Jamieson, A. C. S. Monograph Series, 1932, pages 129-130, Chemical Catalogue Co., 419 Fourth Avenue, N. Y., N. Y.)

Class 2.-Water-soluble aliphatic saturated polyalcohols having over four carbon atoms and at least 2 hydroxy groups and a melting point preferably under C.

Examples-Polyethylene glycols of various molecular weights from 200 to 1,000.

Class 3.-Water-soluble aliphatic saturated primary or secondary amines with two or more amino groups or one amino group and'one or more hydroxy groups.

Examples-Ethylene diamine; diethylenetriamine; triethylenetetramine; tetraethylenepentamine; mono-, and di-ethanolamine; mono-, and di-propanolamines; butylmonoand di-ethanolamines; 2 methyl, 2 amino, 1 propanol; and aminoethylethanolamine.

'In the preferred procedure in producing detergents, emulsifiers and wetting agents, in the first step a fatty acid (one mol) and a polyetwlene glycolU/a to one mol) are heated together with an acid catalyst, such as butyl naphacid is in the range of 30% to 50% by titration (the original free fatty acid of mixtures before heating varies from 70% up to 90%). The product at this stage appears to consist predominantly of diesters and free fatty acid with a relatively small proportion of mono-esters.

In the second step, an aliphatic amine to 2 mols) is then added slowly and the temperature increased to the range of 120 C. to 130 C. The mixture is held at this temperature for 3 to 4 hours or until such time as the free fatty acid is to During this step, the mixture usually becomes alkaline due to the addition of the amine. In some cases, the addition of a small amount of caustic soda or other alkali is desirable at the start to insure the neutralization of the acid catalyst used in the first step and to impart a definite degreeof alkalinity in the second step. In general, if a higher proportion of the polyhydric alcohol is used in the first step, a lower proportion of the amine may be used in the second step and vice versa.

To give some typical examples of the preferred procedure involving combining the fatty acid and the polyethylene glycol in the first step (all parts being by weight):

Example I 282 parts of a low titre olelc acid and 100 parts of a polyethylene glycol having an average molecular weight of 400 are mixed together at a temperature of 110 C. to 115 C. and 1 to 2 parts of an alkylated aromatic sulfonic acid are added. After one hour at this temperature, the free fatty acid content of the mixture is reduced to approximately 50%.

Then the temperature of the mixture is raised to 120 C. to 125 C. and a mixture of 65 parts of diethanolamine and 38 parts of monoethanolamine are added. The heating is then continued at this temperature for 2 to 2 hours or until such time that the free fatty acid content of the mixture is reduced to approximately 20% The resultant composition, when cooled to room temperature, consists of a brown viscous liquid which is useful as a detergent and emulsifying agent in textile wet processing operations. 7 g Example II 228 parts of myristic acid are heated to 100 4 added slowly over a period of about an hour. An esterification catalyst such as an alkylated naphthalene sulionic acid is then added in the amount of 1 to 2 parts and the heating continued for 2 to 3 hours or until one-half of the lauric acid has been esterified.

The temperature is then raised to 125 .C. to 130 C. and 105 parts of diethanolamine are added over a one hour period. The heating is then continued for about 2 hours or until the acid number of the mixture is in the range of to 40.

The resulting product is a dark amber liquid which gives clear solutions in water but hazy solutions in acids. This product has been found to be an eflicient wetting agent.

Example IV 114 parts of myristic acid and 200 parts of polyethylene glycol having an average molecular weight of 400 are mixed and heated at 110 C. to 115 C. for an hour in the presence of a small amount of an alkyl aromatic sulfonic acid. Tim temperature is then raised to between 130' C.

and 135 C. and 20 parts of tetraethylene pentamine are added and the heating is continued for 2 hours.

The resulting product is a brown viscous liquid which is useful as a wetting and emulsifying agent. a

Example V 86 parts of capric acid and 100 parts of a polyethylene glycol having an average molecular weight of 400 are mixed together. Then a small and heating continued until acid numberdrops to 25 to 30, requiring about 2% hours.

C. to 110 C. and 100 parts ofa polyethylene glycol having an average molecular weight-of 200 are added along with about one part of Y a butyl naphthalene sulfonic acid. The temperature is raised to about 115 C. and this temperature is maintained until approximately of the fatty acid has been esterifled. This procedure ordinarily requires from I to 2 hours. The temperature is then raised to between 125 C. and 130 C. and 133 parts of diisopropanolamine are added slowly over the course of about one hour. The reaction mixture is held at this temperature for an additional 4 to 5 hours or until such time as the acid number is in the range of 35 to 40.

The resulting product is a dark amber viscous liquid which is useful as a wetting agent and also useful as a detergent in scouring textiles.

Example III 200 parts of lauric acidare heated to C.

The resulting product is a soft brown paste which has good detergent qualities and is a highly efiicient wetting agent. g

The following examples set forth the alternative procedure in which the fatty acid is combined with the amine in the first step.

' Example v1 210 parts of coconut oil fatty acids are heated to C. to C. and 205 parts of diethanolamine are then added slowly. After about eight hours of continued heating at this temperature. with constant stirring, the temperature is then lowered to 110 C. to 115 C. and 50 parts of a polyethylene glycol having an average molecular weight of 1,000 are added. The heating is continued to maintain this temperature until the acid number of the mixture drops to about 35 to 40. The total time required for this entire operation is 10 hours.

The resulting product is a dark amber-viscous liquid which gives practically clear solutions in water at all concentrations. This product is a very effective wetting agent and also has excellent detergent properties, particularly for wool.

Example VII .210 parts of coconut oil fatty acids and average molecular'weight of 600 are added. Theassure 8 pera ure is maintained at 110' C. to 115' C. for about an hour.

The product obtained by this reaction is a soft, light tan solid which is useful as a textile detergent and has good emulsifying properties.

In general, in the preferred procedure of Examples I to V a fatty acid having 10 to 18 carbon atoms and a polyethylene glycol of a molecular weight of 200 to 1,000 are heated at 110 C. to 115 C. with an acid catalyst until about one-half of the fatty acid is esterined as a first step. Then as a second step, the temperature is raised to 120 C. to 130 C. and a primary or a secondary aliphatic water-soluble amine is added and the heating continued desirably for a longer period until the acid number of the mixture drops to 80 to 50. In the alternative procedure of Examples VI and VII; the amine may be added in the first step and the polyethylene glycol in the secand step, the temperature is lower and the time of treatment is shorter in the second step. Usually an excess of amine is used which gives the resulting product an alkaline reaction. It has been found that primary and secondary amines give far superior results to tertiary amines, in the processes described and for the purposes of this invention;

The tertiary amines do not produce commercially satisfactory wetting and detergent products, as contrasted to the primary and secondary amines which produce highly eflicient products.

To give an outline of the procedure of the above examples:

6 hours and themwith a water soluble alkanolaminc at 120 C. to 130 C. for 8 to 4 hours.

3. A process of making a detergent which comprises combining a high molecular weight fatty acid'having 8 to 24 carbon atoms with a polyethylene glycol at 100 C. to 120 C. for $5 tolt hours and then with a water soluble polyaikylene polyamine at 120 C. to 130 C. for 3 to 4 hours.

4. A process of making a detergent which comprises combining a high molecular weight fatty acid having 8 to 24 carbon atoms with a polyethylene glycol at 100 C. to 120 C. for l to 1% hours and then with a water soluble amine at 120 C. to 130 C. for 8 to 4 hours and then neutralizing with a low molecular weight fatty acid.

5. A process of making a detergent which comprises combining a high molecular weight fatty acid having 8 to 24 carbon atoms with a polyethylene glycol at 100 C. to 120 C. for $5 to 1% hours and then with a water soluble aliphatic amine at 120 C. to 130 C. for 3 to 4 hours and then alkylating the resultant product.

6. A process of making a detergent which comprises combining a high molecular weight fatty acid having 8 to 24 carbon atoms with a polyethylene glycol at 100 C. to 120 C. in the presence of an soluble aliphatic amine at 120 C. to 130 C. for 3 to 4 hours.

7. A process of making a detergent which comprises heating a high molecular weight fatty acid having 8 to 24 carbon atoms with a polyethylene glycol at 100 C. to 115 C. in the presence of an 1 Time and Temperature Rump]: Kiw Amine Properties First Step Second Step I Oleio 1 mol. 400, 34 mol Dietbanolamine, Monoetha- 110 C.115 0., 120 0.-125 0 Def ent. nolamlne, 1% mols. 11l hrs. z-zis hl'S. amifi'imer. II M ti 1 mo]. 200, 36 mol Diiso ro olamine, linoL. 100 C.-1l5 0. 125 C.-l 0. Watt A t.

m p pm 1-2 hrs. 4-5 hrs. mafia? III Laurie, 1 moi... 200, is me] Dlethanolamine, 1 mol 110 C.115 0., 125 C.130 0., Wetting Agent.

3-4 hrs. 3 hrs. IV M sticl mol- 400 1mol... Tetraeth lene pentsmine 110 O.-1l5 0. 130 C.-135 C. Wett A ent.

s moL 1 hr. 2% hrs. Emul 115; Agent. V Ca do me]... 400, mol Aminoeth l-ethanoiaminc 110 C.-115 0. 125 C.-130 0. Watt Agent. 4 moi. y 1% hrs. 2% hrs. VI Coconut, 1 moL. 1,000, Ho mcl. Dlegi ang i minzg 13001251113031: l2g 8C -;1 25 0., 11220 1 15" 0., g e t ti y ggent.

step), 2 mols. I C nut,1 11:01.. 000, mol H drox eth i-eth lenedia- 120 0.-125 0. 110 O.-ll6 C. Detergent. vn no uns om ined zvith fat- 5-0 hrs. 1-2 hrs. I Emulsifler.

ty geld in first step), 1% mo Since certain changes may be made in the above textile assistants and process for manufacturing the same and different embodiments of the invention could be made without depart ing from the scope thereof, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

What is claimed is:

l. A process of making a detergent which comprises combining a high molecular weight fatty acid having 8 to 24 carbon atoms with a polyethylene gylcol at 100 C. to 120 C. for to 1 V. hours and then with a water soluble saturated aliphatic amine at 120 C. to 130 C. for 3 to 4 hours.

2. A process of making a detergent which comprises combining a high molecular weight fatty acid having 8 to 24 carbon atoms with a polyethylene glycol at 100 C. to 120 C. for it to 1% bination of a acid catalyst until about A of the fatty acid is esterifled and then heating the resultant product at 120 C. to 130 C. with a water soluble aliphatic amine until the acid number drops to about 30 to 50.

8. A process of making a detergent which comprises heating one moi of a high molecular weight fatty acid having 8 to 24 carbon atoms with /20 to one moi of a polyethylene glycol having a molecular weight of 200 to 1000 at C. to C. in the presence of an acid catalyst until about of the fatty acid is esterified to produce a mixture of diesters and free fatty acid with a relatively small proportion of mono-esters and then heating the resultant product at C. to C. with M to two mols of a water soluble aliphatic amine until the acid number drops to about 30 to 50.

9. A detergent product consisting of the comwater-soluhle saturated aliphatic acid catalyst and then with a wateramine with the combination of a high molecular weight fatty acid and a polyethylene glycol produced according to the process of claim' 1.

10. A detergent product consisting of the combination of "awater-soluble saturated aliphatic amine'with the combination or a high molecular weight fatty acid and a polyethylene glycol produced according to the process of claim 8.

r ALTON A. COOK.

IRASAPERB.

amnncns cmm The following references are oi. record in the nle of this patent:

UNITED STATES Pam-rs Number Name Date 2,231,754 De Groote et a1. Feb. 11. m1 2,381,185 Engelmann et a1. Oct. 24, 1944 

